JP2961613B2 - Vinyl chloride resin composition - Google Patents

Description

The present invention relates to a stabilized hard vinyl chloride-based resin composition, and more specifically, an epoxy compound having a melting point of 50 ° C. or more, an organotin-based stabilizer and The present invention relates to a hard vinyl chloride resin composition stabilized by adding a metal perchlorate.

[Conventional technology and problems]

Vinyl chloride resin is inexpensive, and has features such as excellent weather resistance, moldability, and gas barrier properties.
Conventionally, films, sheets, and various molded products have been widely used.However, when performing heat processing, it is easy to cause thermal decomposition mainly due to dehydrochlorination, and as a result, the mechanical properties of processed products deteriorate, The color tone deteriorates, resulting in significant disadvantages. In order to avoid such disadvantages, it is necessary to add one or several kinds of heat stabilizers to the vinyl chloride resin to suppress deterioration in the processing step.

Conventionally, various organic acid metal salts, organic tin compounds and the like have been used for such purpose. As a result, almost satisfactory results were obtained in terms of thermal stability.

However, in recent years, these metal salts, particularly cadmium salts or lead salts, have serious toxicity problems, and their use has been limited.

For this purpose, it has been proposed to use various metal salts other than cadmium salts or lead salts in various combinations, for example, Ba / Zn system, Ca / Zn system and Ba / Ca / Zn system. However, the performance of these combinations is not yet sufficient, and the use of various stabilizing aids such as epoxy compounds, polyhydric alcohols, organic phosphorus compounds, organic sulfur compounds, phenol compounds, and β-diketone compounds has been proposed. However, it was not enough, and further improvement was desired.

In addition, the combination of the above metal salt and epoxidized soybean oil has a drawback of lowering the softening point when a hard or semi-hard vinyl chloride resin is blended, although it provides a certain degree of heat stabilizing effect. Furthermore, aminocrotonates have poor compatibility with vinyl chloride resins,
Bloom tends to occur. Further, although dehydroacetic acid improves initial coloration, it does not have a long-term stabilizing effect.

[Means for solving the problem]

The present inventors have conducted intensive studies in order to improve the thermal stability which is a drawback of the hard vinyl chloride resin, and as a result, the melting point was
The present inventors have found that thermal stability can be remarkably improved by using an epoxy compound at 50 ° C. or higher, an organotin-based stabilizer and a metal perchlorate in combination, and have reached the present invention.

That is, the present invention relates to 100 parts by weight of a vinyl chloride resin, 0.1 to 5 parts by weight of an epoxy compound having a melting point of 50 ° C. or more, 0.01 to 10 parts by weight of an organotin stabilizer, and 0.01 to 5 parts by weight of a metal salt of perchlorate. An object of the present invention is to provide a stabilized vinyl chloride resin composition obtained by transferring parts by weight.

Hereinafter, the present invention having the above gist will be described in more detail.

Examples of the epoxy compound having a melting point of 50 ° C or more used as a stabilizer in the present invention include tris (epoxypropyl) isocyanurate (melting point 90 to 125 ° C), hydroquinone diglycidyl ether (melting point 80 to 120 ° C), terephthalic acid Acid diglycidyl ester (melting point 108 ° C), 4,4'-sulfobisphenol polyglycidyl ether (melting point 11
9-167 ° C), N-glycidyl phthalimide (melting point 95-99)
C), a glycidyl (meth) acrylate-based resin having a melting point of 90 to 120 ° C, for example, at least one polymer of glycidyl acrylate and glycidyl methacrylate, or at least one of glycidyl acrylate and glycidyl methacrylate, and methyl acrylate, methyl methacrylate, Alkyl (meth) acrylates such as ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, styrene, α-
Aromatic vinyl compounds such as methylstyrene, acrylonitrile, methacrylonitrile, ethylene, copolymers with at least one copolymerizable monomer selected from ethylene, vinyl acetate, and the like.Especially, epoxy having a melting point of 70 ° C. or more Compounds are preferred.

Examples of the glycidyl (meth) acrylate resin having a melting point of 90 to 120 ° C. include glycidyl methacrylate (GMA) homopolymer, GMA / methyl methacrylate (MMA) copolymer (75:25), and GMA / MMA copolymer. Polymer (50: 5
0), GMA / MMA copolymer (25:75), GMA / ethyl methacrylate (EMA) copolymer (75:25), GMA / methyl acrylate (MA) copolymer (75:25), GMA / MA Copolymer (80: 2
0), GMA / ethyl acrylate (EA) copolymer (75: 2
5), GMA / styrene (St) copolymer (60:40), GMA / St / M
MA copolymer (30:40:30), GMA / St / MMA copolymer (15:50:
35), GMA / St / MMA / EA copolymer (30: 24: 23: 23), GMA acrylonitrile (AN) / St copolymer (10:45:45), GMA / A
N / St copolymer (20:40:40), glycidyl acrylate (GA) homopolymer, GA / MMA copolymer (50:50), etc. These have a number average molecular weight of about 3000 or more. is there.

Epoxy compounds that are liquid at room temperature, such as the normal diglycidyl ether of isopropylidene diphenol, lower the heat distortion temperature of hard vinyl chloride resins, whereas epoxy compounds that are solid at room temperature lower the heat deformation temperature. In addition, it has a very specific effect in that the thermal stability is significantly improved.

The amount of the epoxy compound having a melting point of 50 ° C. or more is 0.1 to 5 parts by weight, more preferably 0.3 to 5 parts by weight, per 100 parts by weight of the vinyl chloride resin.

Examples of the metal salt of perchloric acid used in combination with the epoxy compound having a melting point of 50 ° C. or higher according to the present invention include, for example, Group Ia metal salts such as sodium, potassium and lithium, and calcium, magnesium and barium. II group a metal salts,
Examples thereof include zinc salts and aluminum salts.Also, hydrotalcite, perchloric acid-treated hydrotalcite obtained by treating a basic inorganic double salt such as zinc-modified hydrotalcite with perchloric acid, and the like may be used. Of these metal salts of perchloric acid, Group IIa metal salts are particularly preferred because of their high stabilizing effect.

The addition amount of these metal perchlorates is preferably 0.01 to 5 parts by weight, more preferably 100 parts by weight of the vinyl chloride resin.
It is 0.01 to 3 parts by weight.

Examples of the polyvinyl chloride resin used in the present invention include vinyl chloride homopolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and vinyl chloride. -Propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-urethane copolymer, vinyl chloride-acrylic acid ester copolymer, chloride Vinyl-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, chloride Vinyl-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-maleate copolymer , Vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride copolymer such as vinyl chloride-maleimide copolymer, and the above resin and polyethylene, polypropylene, polybutene, poly-3-methylbutene Α-
Polyolefins such as olefin polymers or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and copolymers thereof, polystyrene, acrylic resin, polyurethane, styrene and other monomers (for example, maleic anhydride, butadiene, Copolymers with acrylonitrile), acrylonitrile-styrene-butadiene copolymer, acrylate-styrene-butadiene copolymer, and methacrylate-styrene-butadiene copolymer blends.

These vinyl chloride resins may be those obtained by any of conventionally known polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization.

Further, by adding a metal salt of a carboxylic acid, an organic phosphoric acid or a phenol to the vinyl chloride resin composition according to the present invention, the heat stabilizing effect is further increased. Examples of the carboxylic acids constituting the metal (Li, Na, K, Ca, Ba, Mg, Sr, Zn, Sn) salts of these carboxylic acids, organic phosphoric acids or phenols include caproic acid, caprylic acid,
Pelargonic acid, 2-ethylhexyl acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid,
12-hydroxystearic acid, chlorostearic acid, 12
-Ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linoleic acid, oleic acid, arachinic acid, behenic acid, erucic acid, brassic acid and similar acids and tallow fatty acids, coconut oil fatty acids, tung oil fatty acids, soy oil fatty acids and Mixtures of the above naturally occurring acids such as cottonseed oil fatty acids, benzoic acid, pt-butyl benzoic acid, ethyl benzoic acid, isopropyl benzoic acid, toluic acid, xylic acid, salicylic acid, 5-t-octyl salicylic acid, naphthenic acid , Monocarboxylic acids such as cyclohexanecarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, Chlorphthalic acid, aminophthalic acid, maleic acid, fumaral , Citraconic acid, metaconic acid, itaconic acid, monoesters of divalent carboxylic acids such as aconitic acid.

Examples of the organic phosphoric acids include mono- or dioctyl phosphoric acid, mono- or di-dodecyl phosphoric acid, mono- or di-octadecyl phosphoric acid, mono- or di (nonylphenyl) phosphoric acid, nonylphenyl phosphonate, stearyl phosphonate, and the like. .

Further, as phenols, phenol, cresol, ethylphenol, cyclohexylphenol,
Nonylphenol, dodecylphenol and the like can be mentioned.

Examples of the organotin-based stabilizer used as an essential component of the present invention include, for example, mono- or dialkyltin compounds such as mono- or dimethyltin-, mono- or dibutyltin- or mono- or dioctyltin compounds. Specifically, sulfides, oxides or sulfide-oxides of mono- or dialkyltins; carboxylates such as octoate, laurate, malate-laurate, stearate, isostearate, crotonate, oleate and basic laurate of dialkyltin; dialkyltin Cyclic maleates or malate polymers; butyl maleate, octyl malate, malate-octyl malate, stearyl malate, oleyl maleate, basic butyl maleate, etc. Alkyl mercaptides such as dialkyltin octyl mercaptide, lauryl mercaptide and stearyl mercaptide; isooctylthioglycolate, 2-ethylhexylthioglycolate, tetradecylthioglycolate, isooctylthio of mono- or dialkyltin; Thioglycolic acid ester salts such as glycolate-sulfide; mono- or dialkyltin thiopropionate salts such as isooctylthiopropionate, 2-ethylhexylthiopropionate, tetradecylthiopropionate; mono- or dialkyltin And mercaptoethanol ester salts such as 2-mercaptoethyl oleate. Among these organotin-based stabilizers, particularly, malate-based, ester-malate-based and thiocarboxylic acid ester salts The preferred stabilizers.

The amount of these organic tin-based stabilizers is 0.01 to 10 parts by weight, more preferably 100 parts by weight of the vinyl chloride resin.
0.1 to 5 parts by weight.

In addition, the composition of the present invention includes inorganic metal salts such as hydrotalcite; higher fatty acids such as stearic acid, higher alcohols such as stearyl alcohol, montan wax, paraffin wax, waxes such as polyethylene wax, stearic acid amide, Lubricants such as amides such as methylenebisstearic acid amide and ethylenebisstearic acid amide can also be added, and if necessary, pigments, dyes, fillers, antistatic agents, flame retardants, etc. Can also.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1 In order to see the effect of the combination of the epoxy compound having a melting point of 50 ° C. or more, a metal perchlorate and an organotin-based stabilizer of the present invention, kneading was performed with a roll of 190 ° C. in the following formulation. Thus, a sheet was prepared.

This sheet was placed in a gear oven at 190 ° C., and the thermal stability (time until significant discoloration) was measured.

The sheet was pressed at 190 ° C. for 4 minutes to prepare a test piece, and the Vicat softening point of the test piece was measured according to JIS K-6740.

 The results are shown in Table 1 below.

(Compound) PVC (TK-1000) 100 parts by weight Stearyl alcohol 0.3 Polyethylene wax 0.3 Blenmer CP-50M 1.5 (Glycidyl methacrylate resin manufactured by NOF) Barium perchlorate 0.15 Organotin stabilizer (Table 1) 0.3 [Effects of the Invention] From the results of each of the above examples, the combined use of an epoxy compound having a melting point of 50 ° C. or higher, an organotin-based stabilizer and a metal perchlorate improves the thermal stability of a hard vinyl chloride-based resin. It is clear that the copolymer has an extremely large effect and does not lower the softening point of the copolymer.

On the other hand, an epoxy compound which is liquid at room temperature not only has a small effect of improving the thermal stability, but also lowers the softening point of the vinyl chloride resin, so that it is not suitable as a stabilizer for the resin.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 27/06 C08K 3/24 C08K 5/57

Claims (1)

(57) [Claims] 1. An epoxy compound having a melting point of 50 ° C. or more, 0.01 to 5 parts by weight, an organotin stabilizer, 0.01 to 10 parts by weight, and a metal perchlorate 0.01 to 5 parts by weight based on 100 parts by weight of a vinyl chloride resin. A rigid vinyl chloride resin composition obtained by adding